US20020011463A1

US20020011463A1 - Isotropic dry cleaning process for noble metal integrated circuit structures

Info

Publication number: US20020011463A1
Application number: US09/768,494
Authority: US
Inventors: Peter Buskirk; Frank DiMeo; Peter Kirlin; Thomas Baum
Original assignee: Advanced Technology Materials Inc
Current assignee: Hanger Solutions LLC
Priority date: 1997-11-10
Filing date: 2001-01-24
Publication date: 2002-01-31
Also published as: US20070134417A1; KR100549680B1; US7605093B2; US6709610B2; AU1520299A; EP1029106A4; US6340769B1; WO1999024635A1; US6254792B1; KR20010031981A; JP2003517515A; US20020062037A1; US7226640B2; US6018065A; EP1029106A1

Abstract

A method for removing from a microelectronic device structure a noble metal residue including at least one metal selected from the group consisting of platinum, palladium, iridium and rhodium, by contacting the microelectronic device structure with a cleaning gas including a reactive halide composition, e.g., XeF₂, SF₆, SiF₄, Si₂F₆or SiF₃and SiF₂radicals. The method may be carried out in a batch-cleaning mode, in which fresh charges of cleaning gas are successively introduced to a chamber containing the residue-bearing microelectronic device structure. Each charge is purged from the chamber after reaction with the residue, and the charging/purging is continued until the residue has been at least partially removed to a desired extent. Alternatively, the cleaning gas may be continuously flowed through the chamber containing the microelectronic device structure, until the noble metal residue has been sufficiently removed.

Description

GOVERNMENT RIGHTS IN INVENTION

[0001] Some aspects of this invention were made in the performance of U.S. Government Contract No. DAA HOI 96-C-RD35, “BaSrTiO₃Etching for Advanced Microelectronic Devices.” The U.S. Government has certain rights in the invention hereof.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to an isotropic dry cleaning process for noble metal integrated circuit structures.

2. Description of the Related Art

Thin films of noble metals (Pt, Pd, Ir, Rh) have become technologically important in integrated circuits (ICs) as electrodes for ferroelectric and high ∘ thin films in FeRAMs, DRAMs, RF and microwave MMICs, pyroelectric IR focal plane detector arrays, etc.

The absence of viable dry etching techniques for submicron patterning of these electrodes is a chronic problem that has threatened to retard or even prevent widespread use of these materials. The present dry-etching approaches utilize plasmas for reactive ion etching (RIE), are chlorine-based, and result in significant residue being left on the microelectronic device structure after the etch process has been completed.

Depending on the type of structure that is being formed by the patterning step, this post-etch residue may result in short circuiting, undesired topography or other deficiencies in the operation of the circuit element in subsequent use of the product microelectronic device. Prevention of the formation of such residues may be achieved in some instances by manipulating the reactive ion etching (RIE) process parameters, but such process manipulation results in undesirable sidewall slopes in the microelectronic device structure that effectively prevent useful submicron capacitors from being fabricated.

Alternatively, the residue resulting from RIE can be removed by wet rinsing techniques, after the etch process has been completed. Wet rinsing techniques are however generally unsatisfactory, because a significant fraction of the residue may be transported in suspension in the rinse media, allowing a small fraction of the residue solids to redeposit on the wafer, and thereby reducing device yield.

Further, in some microelectronic device structure geometries, the residue may not be removed using wet rinsing methods.

Another drawback of wet rinsing methods is the need for a separate process tool to implement the wet rinsing clean-up, which adds to the capital equipment and operating costs of the process system.

It would therefore be a significant advance in the art of integrated circuit device fabrication, in which noble metal films are formed on the device substrate as electrodes or other structural components of the device, to provide an effective cleaning process for removing unwanted residues on the integrated circuit structure after etching or other process fabrication steps.

SUMMARY OF THE INVENTION

The present invention relates to a method for removing noble metal residue from a microelectronic device structure during the fabrication thereof, by contacting the microelectronic device structure with a gas-phase reactive halide composition, e.g., XeF ₂, SF₆, Si₂F₆, SiF₄, or SiF₂and/or SiF₃radicals, for sufficient time and under sufficient conditions to at least partially remove the noble metal residue.

Such “dry clean” method of the invention effects an isotropic dry etching of the noble metal residue for removal thereof. The isotropic dry etching is carried out under low-pressure exposure of the noble metal residue to the reactive halide gas.

The reactive halide may comprise any suitable halide substituent, e.g., fluorine, bromine, chlorine, or iodine, with fluorine generally being most preferred. The reactive halide agent may itself comprise the reaction product of an initial reaction, such as the reaction of XeF ₂with silicon to form SiF₂and/or SiF₃radicals as the reactive halide agent. In this manner SF₆, SiF₄or Si₂F₆may be used with an activation source (ion beam, electron beam, ultra violet or laser) to produce the reactive radical species.

The invention contemplates two main cleaning techniques for using the reactive halide gas as an isotropic noble metal etch agent to remove residual noble metal deposits from the microelectronic device structure.

The first technique is a batch contacting method wherein a chamber containing the microelectronic device structure is evacuated and backfilled with the reactive halide gas or a mixture of the reactive halide gas and other gas(es), either inert or reactive. After the reactive halide is allowed to react for a predetermined amount of time, the chamber is evacuated and backfilled again with fresh cleaning gas. The evacuation pressure can be less than or equal to 50 mTorr. The backfill pressure can be from about 50 mTorr to about 2 Torr, the exposure time can be from about 10 seconds to about 10 min, and the number of exposure cycles is not limited, but will depend on the amount of material to be removed.

The second technique using the reactive halide gas as an isotropic etch agent is a continuous gas flow method. In this technique, a steady state flow of the reactive halide gas, e.g., XeF ₂, SF₆, Si₂F₆or SiF₄, is introduced to the chamber containing the microelectronic device structure to be cleaned. Either pure reactive halide gas or a mixture of the reactive halide and other gas(es), either inert or reactive, may be used. The partial pressure of the reactive halide gas can be from about 50 mTorr to about 2 Torr and total flow rate of the reactive halide gas can be from about 1 standard cubic centimeter per minute (sccm) to about 10 standard liters per minute (slm).

In either case of batch or continuous operation, the microelectronic device structure to be cleaned may be held at temperatures in the range of from about −50° C. to about 200° C.

In the foregoing methodology, the reactive halide gas may for example comprise a XeF ₂vapor. Such vapor may be obtained from the sublimation of XeF₂solid crystals. XeF₂will sublime at room temperature, but may be heated to increase the rate of sublimation.

Additionally, the XeF ₂may first be reacted with elemental silicon, and the resultant reaction product used as the etching gas. It is known that XeF₂etches silicon to produce SiF₄, Si₂F₆and SiF₂and SiF₃radicals.

The reactive halide composition may also be produced in an upstream plasma, e.g., SiF ₂and SiF₃radicals may be formed by passing SiF₄gas through a remote plasma.

The method of the invention is usefully employed for removal of noble metal residues comprising Ir, Rh, Pd and/or Pt, and may be utilized for cleaning hybrid electrodes comprising alloys or combinations of such metals, as well as alloys or combinations of one or more of such metals with other (non-noble) metals.

Other aspects, features and embodiments of the invention will be more fully apparent from the ensuing disclosure and appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a process flow of a fabrication sequence embodying the method of the present invention, in one aspect thereof. [0024]
FIG. 2 is a schematic representation of a process flow of an alternative method embodiment of the invention. [0025]
FIG. 3 is a schematic representation of a process flow for yet another method embodiment of the present invention.[0026]

DETAILED DESCRIPTION OF THE INVENTION AND PREFERRED EMBODMENTS THEREOF

The disclosure of U.S. patent application Ser. No. 08/966,796 filed Nov. 10, 1997 in the names of Thomas H. Baum and Frank DiMeo, Jr. for “METHOD FOR ETCH FABRICATION OF IRIDIUM-BASED ELECTRODE STRUCTURES,” is incorporated herein by reference in its entirety. [0027]
In accordance with the method of the present invention, noble metal residue is removed from a microelectronic device structure including same, by contacting the microelectronic device structure with a gas-phase reactive halide composition, e.g., XeF[0028] ₂, SF₆, SiF₄, Si₂F₆, or SiF₃and/or SiF₂radicals for sufficient time and under sufficient conditions to at least partially remove the noble metal residue.
The method of the invention may be advantageously used to remove residue from a microelectronic device structure, subsequent to reactive ion etching of noble metal electrode films thereon, for patterning of the electrode in the fabrication of the microelectronic device, and/or following chemical mechanical polishing (CMP) of the electrode or a precursor structure therefor. [0029]
As used herein, the term “microelectronic device structure” refers to a microelectronic device or a processing step towards the formation of a structure for the microelectronic device that must be subjected to subsequent processing or treatment steps in order to fabricate the final product device. [0030]
The method of the present invention obviates the deficiencies of the prior art wet rinsing techniques that have been used to remove residues when noble metal structures are formed on the surface of a microelectronic substrate, device or precursor article. [0031]
The isotropic dry etch method of the present invention may be practiced with reactive halogenated compounds such as XeF[0032] 2 and/or other halide compositions as agents for removing extraneous noble metal residues that are present on the microelectronic device structure subsequent to forming noble metal electrodes or other integrated circuit components thereon, and reactive ion etching (RIE) and/or chemical mechanical polishing (CMP) thereof. Alternatively, the removal agent for the noble metal residue may comprise a halogenated radical species such as SiF₂or SiF₃radicals, formed by prior reaction as hereinafter more fully disclosed.
As used herein, the term “noble metal” means a metal of the platinum group, viz., platinum, palladium, iridium or rhodium, as well as alloys and combinations including one or more of such metals, e.g., with other non-noble metal(s). [0033]
The invention contemplates two main cleaning techniques for using the reactive halide gas as an isotropic noble metal etch agent to remove residual noble metal deposits from the microelectronic device structure. [0034]
The first technique is a batch contacting method wherein a chamber containing the microelectronic device structure is evacuated and backfilled with the reactive halide gas or a mixture of the reactive halide gas and other gas(es), either inert or reactive. After the reactive halide is allowed to react for a predetermined amount of time, the chamber is evacuated and backfilled again with fresh cleaning gas. The evacuation pressure can be less than or equal to 50 mTorr. The backfill pressure can be from about 50 mTorr to about 2 Torr, the exposure time can be from about 10 seconds to about 10 min, and the number of exposure cycles is not limited, but will depend on the amount of material to be removed. [0035]
The second technique using the reactive halide gas as an isotropic etch agent is a continuous gas flow method. In this technique, a steady state flow of the reactive halide gas, e.g., XeF[0036] ₂, SF₆, Si₂F₆or SiF₄, is introduced to the chamber containing the microelectronic device structure to be cleaned. Either pure reactive halide gas or a mixture of the reactive halide and other gas(es), either inert or reactive, may be used. The partial pressure of the reactive halide gas can be from about 50 mTorr to about 2 Torr and total flow rate of the reactive halide gas can be from about 1 standard cubic centimeter per minute (sccm) to about 10 standard liters per minute (slm).
In either case of batch or continuous operation, the microelectronic device structure to be cleaned may be held at temperatures in the range of from about −50° C. to about 200° C. [0037]
The dry clean process of the present invention may be carried out at any suitable process condition, including ambient temperature, low temperature and elevated temperature regimes, as well as varying pressure regimes. For example, the cleaning process may be carried out at room temperature conditions involving the sublimation of XeF[0038] ₂to generate an active cleaning agent. XeF₂may also be first reacted with another compound, such as silicon, to generate an active cleaning agent comprising SiF₂or SiF₃radicals.
The time and contacting conditions for the reactive halide etch process may be readily determined by those of ordinary skill in the art. The nature and extent of the etching of the deposited noble metal-based material may be empirically determined while varying the time and/or contacting conditions (such as temperature, pressure, concentration and partial pressure) of the etching agent to identify the process conditions producing a desired etching result. [0039]
In the dry clean of the noble metal residue to etchingly remove same from the microelectronic device structure, the etch rates of the cleaning agent can optionally be enhanced through the use of Lewis-based adducts or electron back-bonding species, e.g., carbon monoxide, trifluorophosphine, trialkylphosphines, etc. These cleaning enhancement agents accelerate the rate of etching by enhancing the volatility of the etch by-products and noble metal (halide)[0040] _xspecies or noble metal (halide radical)_xspecies.
For example, in the case of iridium and/or iridium oxide as the noble metal on the substrate, the step of contacting the iridium-based material with a cleaning gas including the xenon halide etching reagent may be carried out with a cleaning enhancement agent such as carbon monoxide to assist in the volatilization and removal of Ir(X)[0041] _1-6(where X=halide) species from the iridium-based material on the substrate. Where X=chlorine, bromine, fluorine or iodine in the presence of CO serves to enhance the reactant volatility through the formation of (CO)_yIr(X)_1-6. These enhancement agents can be used advantageously for etching Ir in halogen-based plasmas, ion beams and in hybrid etching schemes. Corresponding use of CO or other platinum metal hexafluorides may be utilized to remove other platinum metal residues on semiconductor device structures.
In another example, in the case of iridium and/or iridium oxide as the noble metal on the substrate, the step of contacting the iridium-based material with a cleaning gas including the xenon halide etching reagent may be carried out with a co-etchant such as SF[0042] ₆, Si₂F₆, SiF₄or radical species such as SiF₃and SiF₂to assist in the volatilization and removal of Ir(X)_1-6(where X=silicon halide complex ) species from the iridium-based material on the substrate.
The etching process using the xenon halide etching agent may also be enhanced by use of inert gases. In general, ion beam-assisted, plasma-assisted or photo-assisted techniques may be employed to enhance the etching removal of the noble metal residue, as for example by decreasing the time required for removal, or increasing the extent of removal in a given time, etc. [0043]
In application to the fabrication of specific types of microelectronic device structures, the invention has illustrative utility in the fabrication of capacitor structures. There are three principal types of capacitor geometries and associated processing paths, hereafter referred to as Type 1, [0044] Type 2 and Type 3, in which the method of the present invention offers a significant economic or enabling advantage over the methods of the prior art.
Capacitor arrays in high-density memories (>64 Mb) are typically made by patterning the bottom electrode prior to deposition and patterning of the dielectric and top electrode layers. This is referred to as a Type 1 structure. [0045]
For Type 1 structures, the prior art has used a combination of mechanical liquid agitation and partial dissolution of the residue to “clean up” the noble metal residues. [0046]
The process of the present invention provides an effective alternative to such prior art wet methods for removing noble metal residues from RIE-patterned bottom electrodes. [0047]
The process of the invention is also usefully applied to patterning approaches that define the entire capacitor in one step, including RIE of the entire metal-dielectric stack (Type 2) and chemical mechanical planarization, or chemical mechanical polishing, as such operation is sometimes termed (Type 3). [0048]
In chemical mechanical planarization, capacitors are formed in recesses and excess protruding dielectric and metal is removed by polishing, as more fully described in copending U.S. application Ser. No. 08/975,366 filed Nov. 20,197 in the names of Peter C. Van Buskirk and Peter S. Kirlin for “CHEMICAL MECHANICAL POLISHING OF FeFRAM CAPACITORS,” the disclosure of which hereby is incorporated herein by reference in its entirety. [0049]
Type 1 Capacitor Structures [0050]
As mentioned, this structure is used for very high-density memories, such as those with memory density >64 Mb. Parts of the capacitor are formed on the sidewalls, with potential large increases in capacitor area. [0051]
Referring to FIG. 1 A of the drawings, a Type 1 capacitor array is formed over an array of transistors (not shown), which are contacted preferably by conductive plugs [0052] 1. The conductive plugs are planarized on the surface of the isolation dielectric 2, or subsequent to capacitor formation by etching vias in which conductive plugs are formed, as shown in FIG. 1A.
Next, as shown in FIG. 1B, the [0053] barrier layer 3 and bottom electrode 4 are deposited, using conventional methods such as CVD or sputtering. The bottom electrode is then patterned using RIE or a similar metal etch, as illustrated in FIG. 1C, prior to capacitor dielectric (high ε, ferroelectric, etc.) deposition.
When the electrode is patterned using the predominantly physical mechanism of the impinging ions, involatile material that is sputtered from between the electrodes is redeposited on the sidewalls of the photoresist (or hard mask), and when the mask is removed, the redeposited layers remain. These redeposited features [0054] 5, sometimes characterized as “ears,” are surprisingly robust.
The dry etch cleaning method of the present invention is usefully applied in the fabrication of such Type 1 structure and may be advantageously implemented in-situ in the RIE reactor. As shown in FIG. 1D, the isotropic nature of the dry clean etch effectively removes the ears that were formed by the highly anisotropic RIE process. [0055]
The result is smooth [0056] bottom electrodes 6 that will increase device yield because of the absence of sharp features which would if otherwise present serve to enhance E-fields in the capacitor dielectric. Subsequent processing of the capacitor may then proceed (not shown), comprising dielectric deposition, dielectric patterning, top electrode deposition and patterning, and metallization post oxidizing bake step to complete the formation of the integrated circuit.
In this Type 1 application, the process of the present invention provides a significant economic advantage over prior art wet methods. As mentioned, prior art wet methods, although effective, result in significant decrease in device yield as well as decreased throughput. [0057]
[0058] Type 2 Capacitor Structures
This type of structure is illustrated in FIG. 2 and is usefully employed in lower density memory arrays (<64 Mb), where the area of the capacitor allows sufficiently high capacitance or remenant polarization. [0059]
In the process flow of FIG. 2, the capacitor array is formed on a planar surface of an [0060] isolation dielectric 22, over an array of transistors (not shown). The transistors in this structure are contacted by conductive plugs 21 that have been planarized using CMP or other planarization techniques that are well known in the art. The plug and dielectric structure is illustrated in FIG. 2A.
In this fabrication method, the entire capacitor system of layers, including [0061] conductive barrier 23, bottom electrode 24, dielectric (high ε, ferroelectric, etc.) material 25 and top electrode 26 are deposited sequentially, to produce the structure shown in FIG. 2B.
The capacitors are next defined using conventional microlithography and anisotropic dry etching processes, using either 2 mask levels or 1 mask level. The use of [0062] 1 mask level is the preferred embodiment to produce the structure of FIG. 2C, and is currently the most widespread technique for fabricating FeRAM capacitors.
The comparative advantages of a 2 mask process are well known, and include reducing the tendency for increased leakage currents that occur when a 1 mask approach is used. A 2 mask approach patterns the top electrode (TE) and bottom electrode (BE) to different areas (the TE is smaller), thereby reducing the chance for short circuits at the electrode edge. The 2-mask approach nonetheless is less economical than the 1 mask approach. [0063]
The method of the present invention permits the 1 mask approach to be utilized advantageously without the high level of leakage susceptibility that has been characteristic of prior art products made by such mask approach. [0064]
Due to the predominantly physical nature of the reactive ion etching process, residue collects on the sides of the [0065] capacitor structure 27, making short circuiting more likely. Additionally, sharp features (“ears”) may also be present on the top edges of the top electrode 28, for the same reason as discussed hereinabove in connection with the fabrication of the Type 1 structure.
The process of the present invention is employed to remove the sidewall residue and the “ears”. This process step in FIG. 2D removes metallic conductive residue from the edges of the capacitor, analogous to the use of the dry cleaning method of the invention in the fabrication of the Type 1 structure as described hereinabove. [0066]
In addition to the isotropic dry clean process, a post oxidizing bake may be performed, similar to that described above for the fabrication of the Type 1 structure. The result is a capacitor structure [0067] 29 that is formed with high yield in terms of short circuiting. In addition, the capacitor structure 29 does not have protrusions from the top edges of the top electrode. Such protrusions when present complicate the subsequent isolation of the capacitor array that is required before metallization can be carried out to complete the memory circuits of the structure.
The method of the present invention is of an enabling character in application to the fabrication of the [0068] Type 2 structure, since prior art wet methods do not effectively clean nominally planar surfaces with embedded metallic contamination.
[0069] Type 3 Capacitor Structures
This fabrication technique is shown in the process flow schematically illustrated in FIG. 3. Such fabrication technique may be utilized to completely avoid the need for RIE processes to pattern noble metals and complex oxide thin films, e.g., those comprising PbZrTiO[0070] ₃, SrBiTiO₃and BaSrTiO₃.
The FIG. 3 fabrication technique can be used to fabricate either high or low-density capacitor arrays, since enhanced capacitor area can be obtained from the sidewall contribution, if the aspect ratio of the recesses (depth/width) is large enough. [0071]
Such technique can also be used to fabricate low-density memory arrays, due to the inherent economic advantages of this methodology in minimizing the patterning complexity and the number of steps. [0072]
The capacitor array in the FIG. 3 fabrication method is formed on a planar surface of an [0073] isolation dielectric 32, over an array of transistors (not shown), which are contacted by the conductive plugs 31 illustrated in FIG. 3A. In this fabrication technique, capacitor recesses 33 are formed in a conventional dielectric material 34 (SiO₂or Si₃N₄, for example).
The capacitor recesses are aligned over the conductive plugs [0074] 31, as shown in FIG. 3B. The capacitor recesses 33 will correspond to self-aligned capacitors over such conductive plugs once the patterning of the capacitors is completed.
The entire capacitor system of layers is then deposited sequentially to form the structure shown in FIG. 3C. The respective layers include conductive barrier [0075] 35, bottom electrode 36, dielectric (high ε, ferroelectric, etc.) material 37, and top electrode 38.
The individual capacitors are next defined by chemical mechanical polishing (CMP) of the entire layer system to yield the structure shown in FIG. 3D. Once the structure is formed by CMP there may be [0076] significant metal contamination 39 along the edges of the capacitor on the top surface (which has been planarized) that will result in short circuiting of the capacitor if not removed from the structure. Such metallic contamination is typically due to incomplete removal and smearing of noble metal electrode material during the chemical mechanical polishing operation.
The process of the present invention next is utilized to remove the conductive metallic residue, to produce the structure as shown in FIG. 3E, and thereby allow the capacitors to function as intended. [0077]
In addition to the isotropic dry clean process, a post oxidizing bake may be employed to heal surface and/or subsurface damage to the dielectric (high ε, ferroelectric, etc.) material. Such damage may be either chemical or physical in nature. The post oxidizing bake thereby imparts optimum insulating or ferroelectric properties (depending on the material of construction) to the dielectric material. [0078]
The result is a [0079] capacitor structure 40 shown in FIG. 3E that is formed with high yield (in terms of non-short circuiting device elements), in a highly economical manner. In this application (the fabrication of Type 3 structures), the process of the present invention is enabling in character, since wet cleaning methods of the prior art do not work well to clean planar surfaces with embedded metallic contamination.
Accordingly, while the invention has been described herein with reference to specific features, aspects and embodiments, it will be recognized that the invention may be widely varied, and that numerous other variations, modifications and other embodiments will readily suggest themselves to those of ordinary skill in the art. Accordingly, the ensuing claims are to be broadly construed, as encompassing all such other variations, modifications and other embodiments, within their spirit and scope. [0080]

Claims

1. A method for removing from a microelectronic device structure a noble metal residue including at least one metal selected from the group consisting of platinum, palladium, iridium and rhodium, the method comprising contacting the microelectronic device structure with a gas-phase reactive halide composition to remove the residue.

2. The method according to claim 1, wherein the reactive halide composition comprises XeF₂.

3. The method according to claim 1, wherein the reactive halide composition is selected from the group consisting of SF₆, SiF₄, and Si₂F₆.

4. The method according to claim 1, wherein the reactive halide composition is selected from the group consisting of SiF₂and SiF₃radicals.

5. The method according to claim 1, wherein the contacting is carried out at a temperature from about −50° C. to 200° C.

6. The method according to claim 1, wherein the microelectronic device structure is disposed in a chamber, further comprising: evacuating the chamber, filling the chamber with a cleaning gas comprising the reactive halide composition, and retaining the reactive halide composition in the chamber to react with the residue, to effect removal of the noble metal residue from the microelectronic device structure.

7. The method according to claim 6, wherein the pressure of the chamber upon evacuation is less than or equal to 50 mTorr, the cleaning gas is at a pressure from about 50 mTorr to about 2 Torr, and the reaction time for each fill of cleaning gas in the chamber is from about 10 seconds to 10 minutes.

8. The method according to claim 1, wherein the microelectronic device structure is disposed in a chamber, and a cleaning gas comprising the reactive halide composition is continuously flowed through the chamber to effect the removal of the noble metal residue from the microelectronic device structure.

9. The method according to claim 8, wherein the reactive halide composition is at a vapor pressure from about 50 mTorr to about 2 Torr, and the cleaning gas through the chamber has a flow rate from about 1 standard cubic centimeter per minute to 10 standard liters per minute.

10. The method according to claim 1, wherein the gas-phase reactive halide composition comprises XeF₂and the reactive halide composition comprising XeF₂is generated by an inherent vapor pressure of XeF₂.

11. The method according to claim 1, wherein the gas-phase reactive halide composition comprises XeF₂and the reactive halide composition comprising XeF₂is generated by sublimation of solid crystalline XeF₂.

12. The method according to claim 1, wherein the gas-phase reactive halide composition is selected from the group consisting of SiF₂and SiF₃radicals and the reactive halide composition is generated by reaction of XeF₂with silicon.

13. The method according to claim 1, wherein the gas-phase reactive halide composition is selected from the group consisting of SiF₂and SiF₃radicals and the reactive halide composition is generated by passing SiF₄through an energetic dissociation source.

14. The method according to claim 13, wherein the energetic dissociation source is selected from the group consisting of a plasma source, an ion source, an ultra violet source and a laser source.

15. The method according to claim 1, wherein the noble metal residue comprises platinum.

16. The method according to claim 1, wherein the noble metal residue comprises palladium.

17. The method according to claim 1, wherein the noble metal residue comprises iridium.

18. The method according to claim 1, wherein the noble metal residue comprises rhodium.

19. The method according to claim 1, wherein the noble metal residue comprises iridium and a cleaning gas comprising the reactive halide composition XeF₂.

20. The method according to claim 19, further comprising, contacting the microelectronic device structure with a cleaning enhancement agent to assist in volatilizing and removing the noble metal residue on the microelectronic device structure.

21. The method according to claim 20, wherein the cleaning enhancement agent is selected from the group consisting of Lewis-base adducts and electron back-bonding species.

22. The method according to claim 20, wherein the cleaning enhancement agent is selected from the group consisting of carbon monoxide, trifluorophosphine, and trialkylphosphines.

23. The method according to claim 22 wherein the cleaning enhancement agent comprises an iridium halide species selected from the group consisting of Ir(X)₁, Ir(X)₃, Ir(X)₄and Ir(X)₆, wherein X represents the halide of the reactive halide composition.

24. The method according to claim 19, wherein the cleaning gas further comprising a gas phase reactive halide species selected from the group consisting of SF₆, SiF₄, Si₂F₆and SiF₂and SiF₃radicals and the microelectronic device structure, is further contacted with a cleaning enhancement agent.

25. The method according to claim 24, wherein the cleaning enhancement agent is selected from the group consisting of Lewis-base adducts and electron back-bonding species.

26. The method according to claim 24, wherein the cleaning enhancement agent is selected from the group consisting of carbon monoxide, trifluorophosphine, and trialkylphosphines.

27. The method according to claim 24 wherein the cleaning enhancement agent comprises an iridium halide species from the group consisting of Ir(X)₁, Ir(X)_3,Ir(X)₄and Ir(X)_6,wherein X represents the halide of the reactive halide composition.

28. The method according to claim 1, wherein the contacting of the microelectronic device structure with the gas phase reactive halide composition is carried out with a cleaning enhancement agent and the contacting comprises an enhancement step selected from the group consisting of:

(a) providing an inert gas in the cleaning enhancement agent;

(b) carrying out the contacting in an ion-beam-assisted manner;

(c) carrying out the contacting in a plasma-assisted manner;

(d) carrying out the contacting in a photo-assisted manner and

(e) carrying out the contacting in a laser assisted manner.

29. The method according to claim 1, wherein the noble metal residue comprises iridium, and carbon monoxide is present in the contacting.

30. The method according to claim 1, wherein a hexafluoride compound of the noble metal is present in the contacting.

31. The method according to claim 1, wherein a silicon fluoride compound is present in the contacting.

32. The method according to claim 1, wherein the noble metal residue comprises iridium, and IrF₆is present in the contacting.

33. The method according to claim 1, wherein a Lewis base ligand is present in said contacting, to enhance the removal of the noble metal residue.

34. The method according to claim 1, wherein the microelectronic device structure comprises a capacitor.

35. The method according to claim 34, wherein the capacitor is selected from the group consisting of a Type 1-capacitor structure, a Type 2-capacitor structure and a Type 3-capacitor structure.

36. The method according to claim 1, wherein the contacting of the microelectronic device structure with the reactive halide composition is conducted after reactive ion etching of a noble metal electrode film on the microelectronic device structure.

37. The method according to claim 1, wherein the contacting of the microelectronic device structure with the reactive halide composition is conducted after chemical mechanical polishing of a noble metal electrode film on the microelectronic device structure.

38. The method according to claim 1, wherein the microelectronic device structure comprises a patterned bottom electrode of a capacitor structure, and the contacting is carried out after patterning of the bottom electrode.

39. The method according to claim 1, wherein the microelectronic device structure comprises a Type 2 capacitor structure, and the contacting comprises removing sidewall residue and ears of the capacitor structure.

40. The method according to claim 1, wherein the microelectronic device structure comprises a Type 3 capacitor structure, and the contacting is carried out to remove residue from a chemical mechanical polishing of the Type 3-capacitor structure.

41. A method for removing from a microelectronic device structure a noble metal residue including at least one metal selected from the group consisting of platinum, palladium, iridium and rhodium, the method comprising contacting the microelectronic device structure with gas-phase XeF₂to at least partially remove the noble metal residue.

42. The method according to claim 41, wherein the contacting is carried out at a temperature from about −50° C. to about 200° C.

43. The method according to claim 41 wherein elemental silicon is present with the gas-phase XeF₂in said contacting.

44. The method according to claim 41, wherein the microelectronic device structure is disposed in a chamber, further comprising evacuating the chamber, filling the chamber with a cleaning gas comprising XeF₂, and retaining the cleaning in the chamber to react with the residue, to effect the removal of the noble metal residue from the microelectronic device structure.

45. The method according to claim 44, wherein the pressure of the chamber upon evacuation is less than or equal to 50 mTorr, the cleaning gas is at a pressure from about 50 mTorr to about 2 Torr, and the reaction time for each fill of cleaning gas is from about 10 seconds to about 10 min.

46. The method according to claim 44, wherein elemental silicon is present in the chamber.

47. The method according to claim 41, wherein the microelectronic device structure is disposed in a chamber, and the cleaning gas comprising a gas phase reactive halide composition selected from the group consisting of SF₆, SiF₄and Si₂F₆, is continually flowed through the chamber, in combination with an energetic dissociation source.

49. The method according to claim 47, wherein the energetic dissociation source is selected from the group consisting of a plasma source, an ion source, an ultra violet source and a laser source.

50. The method according to claim 46, wherein the gas phase reactive halide composition is selected from the group of radicals consisting of SiF₂and SiF₃.

51. The method according to claim 47, wherein the gas phase reactive halide composition is selected from the group of radicals consisting of SiF₂and SiF₃.